Flame-retardant agents for thermoplastic products

ABSTRACT

COMPOUNDS USEFUL AS FLAME-RETARDING AGENTS AND HAVING THE FORMULA   R5-P(+)(-R6)(-R7)-R4 .Y(-)   WHEREIN R4 IS CARBOXYALKENYL, CARBOALKOXYALKENYL OR 2CYANOETHYL, R5, R6 AND R7, ARE INDIVIDUALLY ALKYL; ALKENYL; CYANO, HYDROXY, OR CARBOXY SUBSTITUTED ALKYL; ARYL; ARALKYL; VINYL, HALO, POLYHALO, OR NITRO AR-SUBSTITUTED ARALKYL; DIALKYLAMINOALKYL OR CARBOALKOXYALKYL RADICALS AND Y IS ALKYLAMINOALKYL OR CARBOALKOZYALKYL RADICALS AND Y IS BROMINE OR CHLORINE, R5, R6 AND R7 BEING 2-CYANOETHYL AND Y BEING BROMINE WHEN R4 IS 2-CYANOETHYL AND AT LEAST ONE OF R5, R6 AND R7 BEING CYANO SUBSTITUTED ALKYL WHEN R4 IS CARBOXYALKENYL OR CARBOALKOYALKENYL, ARE DISCLOSED.

United States Patent O 3,654,342 FLAME-RETARDANT AGENTS FORTHERMOPLASTIC PRODUCTS Helen Currier Gillham, Princeton, and Allan EllisSherr, Martinsville, N.J., and Harvey Gerald Klein, New York, N.Y.,assignors to American Cyanamid Company, Stamford, Conn.

No Drawing. Application Aug. 13, 1965, Ser. No. 479,599, which is acontinuation-in-part of application Ser. No. 296,364, July 19, 1963.Divided and this application Aug. 19, 1968, Ser. No. 753,739

Int. Cl. C07c 121/28 US. Cl. 260465.8 1 Claim ABSTRACT OF THE DISCLOSURECompounds useful as flame-retarding agents and having the formulawherein R is carboxyalkenyl, carboalkoxyalkenyl or 2- cyanoethyl, R Rand R are, individually, alkyl; alkenyl; cyano, hydroxy, or carboxysubstituted alkyl; aryl; aralkyl; vinyl, halo, polyhalo, or nitroar-substituted aralkyl; dialkylaminoalkyl or carboalkoxyalkyl radicalsand Y is bromine or chlorine, R R and R being 2-cyanoethyl and Y beingbromine when R is 2-cyanoethyl and at least one of R R and R being cyanosubstituted alkyl when R is carboxyalkenyl or carboalkoyalkenyl, aredisclosed.

CROSS-REFERENCES TO RELATED APPLICATIONS This application is adivisional or our copending application, Ser. No. 479,599, filed Aug.13, 1965, Which, in turn, is a continuation-in-part of our application,Ser. No. 296,364, filed July 19, 1963, and now abandoned.

BACKGROUND OF THE INVENTION The use of various materials incorporatedinto thermoplastic resins in order to improve the fiame-retardancethereof has been known in the prior art. Many compounds are commerciallyavailable for such a use, among them being chlorostyrene copolymers,chlorinated parafiin wax with triphenyl stibine, chlorinated paraffinsand aliphatic antimonyl compounds, as well as antimony oxide-chlorinatedhydrocarbon mixtures. A drawback, however, of these compounds has beenthe fact that generally a large amount, i.e. upwards of 35%, of additivemust be incorporated into the resin in order to make it sufiicientlyflameretardant. Also these prior art additives tend to crystallize oroil out of the resin after a relatively short time of incorporation.

SUMMARY We have now found a group of compounds which may be added tothermoplastic resins in relatively small amounts and still result in theproduction of satisfactory flame-retardant compositions while notcrystallizing or oiling out of the resin after incorporation therein.

The production of thermoplastic resin compositions which areflame-retardant, i.e. have high resistance to heat, is of considerablecommercial importance. For example, such articles as castings, moldings,foamed or laminated structures and the like are required, or at leastdesired, to be resistant to fire and flame and to possess the ability toendure heat without deterioration. Typical illustrations of suchapplications can be found in castings for live electrical contacts whichshould not be ignited or deteriorated by heat and sparks.

3,654,342 Patented Apr. 4, 1972 ICC DESCRIPTION OF THE INVENTIONINCLUDING PREFERRED EMBODIMENTS wherein R, R R and R are, individually,alkyl (C -C alkenyl (C -C cyano, hydroxy, imidazolyl, and carboxysubstituted alkyl (C -C aryl (C -C10), aralkyl (C C vinyl, halo,polyhalo, and nitro ar-substituted aralkyl (C -C dialkylaminoalkyl (C -Ccarboalkoxyalkyl (C -C carboxyalkenyl (C -C or carboalkoxyalkenyl (C -Cradicals, and X is a bromine, chlorine or iodine radical.

This invention also relates to various novel compounds having theformula Rfl \R7 wherein R is a carboxyalkenyl radical (Cy-C a 2-cyanoethyl radical, or a carboalkoxyalkenyl radical (C C and R R and Rare, individually, alkyl (C -C alkenyl (C 0 cyano, hydroxy, and carboxysubstituted alkyl (C -C aryl (C -C aralkyl (0 -0 vinyl, halo, polyhaloand nitro ar-substituted aralkyl (C C dialkylaminoalkyl (C -C orcarboalkoxyalkyl (C -C radicals and Y is chlorine or bromine, R R and Rall being 2-cyanoethyl radicals and Y being bromine When R is a2-cyanoethyl radical and at least one of R R and R being cyanosubstituted alkyl when R is carboxyalkenyl or carboalkoxyalkenyl.

The thermoplastic polymers The thermoplastic polymer into which theflame-retardant agents may be incorporated to produce the novelcompositions of the present invention, are generally the vinyl typepolymers wherein the monomeric material is polymerized, by any knownmethod, via the vinyl unsaturation therein. Additionally, however,thermoset type materials may be employed such as the polyester resins,polyurethanes, and the like. Examples of the vinyl type polymers whichmay be used to form our novel compos itions are the vinyl halides, thevinylidene halides, the vinyl acetates, polyvinylbutyral, butadienecopolymers, acrylonitrile-butadiene-styrene polymers, theacrylonitriles, etc. Additionally and preferably, one may incorporatethe flame-retardant agents mentioned above into such polymers as thestyrene polymers, i.e. polystyrene, etc., the u-olefin polymers, such asthe homopolymers and copolymers etc. containing, as the majorconstituent, ethylene, propylene, and the like and the acrylate andmethacrylate polymers produced from monomers having the formula (III) 0wherein R is hydrogen or a methyl radical and R is hydrogen or an alkylradical having from 1 to 6 carbon atoms, inclusive. Examples of monomersrepresented by Formula III include methyl acrylate, ethyl acrylate,npropyl acrylate, isopropyl acrylate, n-butyl acrylate, tbutyl acrylate,isobutyl acrylate, n-amyl acrylate, t-amyl acrylate, hexyl acrylate andtheir corresponding alkyl methacrylates.

Also such polymers as the nylons, e.g. adipic acid-hexamethylenediaminereaction products, the polyformaldehydes, cellulose acetate (and/orbutyrate, etc.), the polycarbonates, i.e. phosgene-bisphenol A reactionproducts, the so-called impact polymers, i.e. rubber-polymer blends suchas blends of polystyrene With 10% of butadienestyrene, etc. may be madeflame-retardant by the incorporation therein of the phosphonium halidesmore specifically discussed hereinbelow and represented by Formulae Iand II.

Additional examples of monomers which may be used to form thethermoplastic vinyl polymers encompassed by the present invention,polymerized either singularly or in combination with each other or withthe other com pounds set forth hereinabove, are such monomers as theunsaturated alcohol esters, more particularl the allyl, methallyl,vinyl, methvinyl, butenyl, etc., unsaturated esters of aliphatic andaromatic monobasic acids such, for instance, as acetic, propionic,butyric, crotonic, succinic, glutaric, adipic, maleic, fumaric,itaconic, benzoic, phthalic, terephthalic, benzoylphthalic, etc., acids;the saturated monohydric alcohol esters, e.g., the methyl, ethyl,propyl, isopropyl, butyl, sec-butyl, amyl, etc., esters of ethylenicallyunsaturated aliphatic monobasic acids, illustrative examples of whichappear above; vinyl cyclic compounds (including monovinyl aromatichydrocarbons), e.g., 0-, m-, and p-chlorostyrenes, -bromostyrenes,-fluorostyrenes, -methylstyrenes, -ethylstyrenes, -cyanostyrenes, thevarious poly-substituted styrenes such, for example, as the various di-,tri-, and tetra-chlorostyrenes, -bromo'styrenes, fluorostyrene's,-methylstyrenes, -ethylstyrenes, -cyanostyrenes, etc., vinyl pyridine,divinyl benzene, diallyl benzene, the various allyl cyanostyrenes, thevarious alphasubstituted styrenes and alpha-substituted ring-substitutedstyrenes, e.g., alpha-methyl styrene, alpha-methyl-paramethyl styrene,etc.; unsaturated ethers, e.g., ethyl vinyl ether, diallyl ether, etc.;unsaturated amides, for instance, N-allyl caprolactam, acrylamide, andN-substituted acrylamides, e.g., N-methylol acrylamide, N-allylacrylamide, N-methyl acrylamide, N-phenyl acrylamide, etc.; unsaturatedketones, e.g., methyl vinyl ketone, methyl allyl ketone, etc.; methylenemalonic esters, e.g., methylene methyl malonate, etc. and ethylene.

Other examples of monomers than can be used as polymers to form theresin portion of our novel flameretardant compositions are the vinylhalides, more particularly, vinyl fluoride, vinyl chloride, vinylbromide and vinyl iodide, and the various vinylidene compounds,including the vinylidene halides, e.g., vinylidene chloride, vinylidenebromide, vinylidene fluoride, and vinylidene iodide, other comonomersbeing added, if needed, in order to improve the compatibility andcopolymerization characteristics of the mixed monomers.

More specific examples of allyl compounds that can be polymerized touseful polymers, useful in the production of our novel flame-retardantcompositions, are allyl alcohol, methallyl alcohol, diallyl carbonate,allyl lactate, allyl alphahydroxyisobutyrate, allyl trichlorosilane,diallyl phthalate, diallyl methylgluconate, diallyl tartronate, diallyltartrate, diallyl mesaconate, the diallyl ester of muconic acid, diallylchlorophthalate, diallyl dichlorosilane, the diallyl ester ofendomethylene tetrahydrophthalic anhydride, triallyl tricarballylate,triallyl cyanurate, triallyl citrate, triallyl phosphate, tetrallylsilane, tetrallyl silicate, hexallyl disiloxane, allyl diglycolcarbonate, etc. Other examples of allyl compounds that may be employedare given, for example, in US. Pat. No. 2,510,503, issued June 6, 1950.

These above mentioned monomers may be polymerized, copolymerized, etc.,in any known manner such as by free-radical generating catalysts,irradiation, anion and cation type catalysts and the like, said methodof polymerization forming no part of the present invention.

The monophosphonium halides As mentioned above, we have discovered theaddition of monophosphonium halides to a thermoplastic resin results inthe production of resinous compositions having excellent flame-retardantproperties. According to the present invention, any monophosphoniumhalide, stable to processing conditions, may be used for this purpose. Apreferred group of phosphonium halides, however, are those representedby Formula I. The monophosphonium halides may be incorporated into theresins in flameretarding amounts, i.e. generally amounts ranging fromabout 1%, by weight, to about 35%, by weight, preferably 5% to 25%, byweight, based on the weight of the polymer, have been found sufiicient.A further group of preferred monophosphonium halide compounds useful inproducing our novel compositions are those wherein three of R, R R and Rare cyanoethyl or phenyl radicals.

These monophosphonium halides can be incorporated into the resin by anyknown method. That is to say, the flame-retardant monophosphonium halideadditive may be added to the resin by milling the resin and the halideon, for example, a two-roll mill, in a Banbury mixer etc., or the halidemay be added by molding the halide and resin simultaneously, extrudingthe halide and resin or by merely blending the resin in powder form withthe halide and thereafter forming the final desired article.Additionally, the monophosphonium halide may also be added during theresin manufacture, i.e., during the monomer polymerization procedure,provided the catalyst, etc. conditions and ingredients of thepolymerization system are inert to the monophosphonium halide.

The monophosphonium halides set forth hereinabove may be produced in anyknown manner without varying from the scope of the present invention.Various methods for the production of phosphonium halides of this typeare disclosed in, for example, articles by Rauhut et al., J. Org. Chem,volume 28, page 473, 1963; Grayson et al., J. Am. Chem. Soc., volume 81,page 4806, 1959; Grayson et al., I. Am. Chem. Soc., volume 82, page3922, 1960; US. Pat. 3,005,013 to Grayson et al., patented Oct. 17,1961; Rauhut et a1. patent application, Ser. No. 211,412, filed July 20,1962 and these articles and patents are hereby incorporated herein byreference.

Those phosphonium halides represented by Formula I may be produced byreacting a compound of the formula II may be produced, among othermethods, by reacting a compound having the formula with a compoundhaving the formula wherein R R R R and Y are as indicated above inregard to Formula II, under the following conditions: heat, to atemperature ranging from about 0 C. to about 150 C., a solution of thehalide and tertiary phosphine in an appropriate solvent, such asbutanol, acetonitrile and the like, for from 1 to 24 hours. Thephosphonium halide is isolated by filtration, in the case of aninsoluble product, by precipitation with ethyl ether or by evaporationof the solvent. Yields usually are from 50% to of the theoretical, saidprocedures, however, forming no part of the present invention.

In any of said procedures wherein an unsaturated radical is present inthe phosphine or the halide, a polymerization inhibitor such ashydroquinene is preferably added to retard the polymerization of thecompound produced.

The imidazolyl compounds may alternatively be prepared by reacting,under the conditions specified above in regard to the othermonophosphonium halides, a compound such as tributylvinylphosphoniumbromide or tricyclohexyl vinylphosphonium bromide, etc., with anappropriately substituted imidazole, e.g., 2-methyl imidazole byrefluxing in a suitable solvent. The products are then recovered byfiltration.

The carboxyalkyl compounds may also be produced via another mechanismaccording to the equations:

The first step is accomplished at 80 to 105 C. under a nitrogenatmosphere for about 3 hours while the second step is conducted at roomtemperature and recovery is by subsequent water evaporation.

Examples of compounds which are represented by Formulae I or II and aretherefore useful in producing the novel compositions of the presentinvention, include tetramethylphosphonium chloride, bromide and iodide,tetraethylphosphonium chloride, bromide and iodide,tetra-n-propylphosphoniurn chloride, bromide and iodide,tetraisopropylphosphonium chloride, bromide and iodide,tetra-n-butylphosphonium chloride, bromide and iodide,tetra-t-butylphosphonium chloride, bromide and iodide,tetraisobutylphosphonium chloride, bromide and iodide,tetrapentylphosphonium chloride, bromide and iodide,tetrahexylphosphonium chloride, bromide and iodide,tetraheptylphosphonimn chloride, bromide and iodide,tetraoctylphosphonium chloride, bromide and iodide,tetravinylphosphonium chloride, bromide and iodide,tetraallylphosphonium chloride, bromide and iodide, tetrapropenyl 1phosphonium chloride, bromide and iodide, tetra 1 butenylphosphom'umchloride, bromide and iodide, tetra 2 butenylphosphonium chloride,bromide and iodide, terta 1 or 2 peutenylphosphonium chloride, bromideand iodide, tetra-L; -2-or-3-hexenylphosphonium chloride, bromide andiodide, tetra-L; -2- or-3-heptenylphosphonium chloride, bromide andiodide, tetra-L; -2-; -3-or-4octenylphosphonium chloride, bromide andiodide, tetracyanomethylphosphonium chloride, bromide and iodide,tetra-2-cyanoethylphosphonium chloride, bromide and iodide, tetra 2cyanopropylphosphonium chloride, bromide and iodide,tetra-B-cyanopentylphosphonium chloride, bromide and iodide,tetr-a-2-cyanohexylphosphonium chloride, bromide and iodide, tetra-4-cyanohexylphosphonium chloride, bromide and iodide, tetra 3cyanoheptylphosphonium chloride, bromide and iodide, tetra 6cyanooctylphosphonium chloride, bromide and iodide,tetrahydroxymethylphosphonium chloride, bromide and iodide,tetra-Z-hydroxyethylphosphonium chloride, bromide and iodide,tetra-Z-hydroxypropylphosphonium chloride, bromide and iodide,tetra-B-hydroxypentylphosphonium chloride, bromide and iodide, tetra 4hydroxyhexylphosphonium chloride, bromide and iodide,tetra-6-hydroxyhexylphosphonium chloride, bromide and iodide,tetra-3-hydroxyheptylphosphonium chloride, bromide and iodide,tetra-8-hydroxyoxtylphosphonium chloride, bromide and iodide,tetracarbo-xymethylphosphonium chloride, bromide and iodide, tetra-Z-carboxyethylphosphonium chloride, bromide and iodide,tetra-Z-carboxypropylphosphonium chloride, bromide and iodide,tetra-3-carboxypentylphosphonium chloride, bromide and iodide,tetra-S-carboxyhexylphosphonium chloride, bromide and iodide, tetra 7carboxyheptylphosphonium chloride, bromide and iodide,tetra-l-carboxyoctylphosphonium chloride, bromideand iodide,tetraimidazolylmethylphosphonium chloride, bromide and iodide, tetra 2imidazolylethylphosphonium chloride, bromide and iodide,tetra-3-imidazolylpropylphosphonium chloride, bromide and iodide,tetra-S-imidazolylpentylphosphonium chloride, bromide and iodide,tetra-Z-imidazolylbutylphosphonium chloride, bromide and iodide,tetra-3-cyanobutylphosphonium chloride, bromide and iodide,tetra-3-hydroxybutylphosphonium chloride, bromide and iodide, tetra 4carboxybutylphosphonium chloride, bromide and iodide,tetra-Z-imidazolylhexylphosphonium chloride, bromide and iodide,tetra-3-imidazolylheptylphosphonium chloride, bromide and iodide, tetra8 imidazolyloctylphosphonium chloride, bromide and iodide,tetraphenylphosphonium chloride, bromide and iodide,tetratolylphosphonium chloride, bromide and iodide,tetraxylylphosphonium chloride, bromide and iodide, tetra amethylphenylphosphonium chloride, bromide and iodide,tetranaphthylphosphonium chloride, bromide and iodide,tetrabenzylphosphonium chloride, bromide and iodide,tetra-2-phenethylphosphonium chloride, bromide and iodide,tetra-a-methylbenzylphosphonium chloride, bromide and iodide,tetra-a-ethylbenzylphosphonium chloride, bromide and iodide,tetra-4phenylbutylphosphonium chloride, bromide and iodide, tetra-5-phenylpentylphosphonium chloride, bromide and iodide, tetra(o, m orp-vinylbenzyl)phosphonium chloride, bromide and iodide, tetra(o, m orp-chloro, bromo, fluoro or iodobenzyl) phosphonium chloride, bromide andiodide, tetra(o, m or p-dichloro, dibromo, difluoro ordiiodobenzyl)phosphonium chloride, bromide, and iodide, tetra(o, m orp-nitrobenzyl)phosphonium chloride, bromide and iodide, tetra(o, m orp-vinyl-2-phenethyl)phosphonium chloride, bromide and iodide, tetra(o, mor pchloro 2 phenethyl), phosphonium chloride, bromide and iodide,tetra(o, m or p-dibromo-Z-phenethyl)phosphonium chloride, bromide andiodide, tetra(o, m or pnit'ro-Z-phenethyDphosphonium chloride, bromideand iodide, tetra(o, m or p vinyl a methylbenzyl) phosphonium chloride,bromide and iodide, tetra(o, m or p fluoro oz methylbenzyl)phosphoniurnchloride, bromide and iodide, tetra(o, m or p trichloroocmethylbenzyl)phosphonimn chloride, bromide and iodide, tetra(o, m orp-nitro-a-methylbenzyl)phosphonium chloride, bromide and iodide,tetranaphthylmethylphosphonium chloride, bromide and iodide,tetra(vinyl, chloro, dibro-mo or nitro arr-substitutednaphthylmethyl)phosphonium chloride, bromide and iodide,tetra(dimethylaminomethyl) phosphonium chloride, bromide and iodide,tetra- (diethylaminomethyl)phosphonium chloride, bromide and iodide,tetra(diethylaminoethyl)phosphonium chloride, bromide and iodide,tetra(butylmethylaminomethyl)- phosphonium chloride, bromide and iodide,tetrakis(car- 'bomethoxymethyl)phosphonium chloride, bromide and iodide,tetrakis(carboethoxymethyl)phosphonium chloride, bromide and iodide,tetrakis(carbomethoxyethyl) phosphonium chloride, bromide and iodide,tetrakis(2- carboethoxyethyl)phosphoniurn chloride, bromide and iodide,tetrakis(3-carboethoxypropyl)phosphonium chlo ride, bromide and iodide,tetralris(2-carbopropoxyethyl) phosphonium chloride, bromide and iodide,tetrakis(carbobutoxymethyDphosphonium chloride, bromide and iodide,tetrakis(3-carbopropoxypropyl)phosphonium chloride, bromide and iodide,tetrakis(carbopentoxymethyl) phosphonium chloride, bromide and iodide,tetrakis(4- carboethoxybutyl)phosphonium chloride, bromide and iodide,tetrakis(carbomethoxyvinyl)phosphonium chloride, bromide and iodide,tetrakis(Z-carbomethoxyallyl)phosphonium chloride, bromide and iodide,tetrakis(carboethoxy.vinyl)phosphonium chloride, bromide and iodide,tetrakis(carbobutoxyvinyl)phosphonium chloride, bromide and iodide,tetrakis(2 carbomethoxy-2-butenyl)- phosphonium chloride, bromide andiodide, tetrakis(2- carbomethoXy-3-pentenyl)phosphonium chloride,bromide and iodide, methyltriphenylphosphonium chloride, bromide andiodide, ethyltriphenylphosphonium chloride, bromide and iodide,propyltriphenylphosphonium chloride, bromide and iodide,benzyltriphenylphcxsphonium chloride, bromide and iodide,p-nitrobenzyltriphenyl hosphonium chloride, bromide and iodide,2,4-dichloroben zyltriphenylphosphonium chloride, bromide and iodide,carboethoxymethyltriphenylphosphonium chloride, bromide and iodide,tris(Z-cyanoethyl)methylphosphonium chloride, bromide and iodide,tris(2-cyanoethyl)-ethylphosphonium chloride, bromide and iodide,tris(2-cyanoethyl)octylphosphonium chloride, bromide and iodide,tris(2-cyanoethyl) allylphosphonium chloride, bromide and iodide,benzyl-tris(2-cyanoethyl)phosphonium chloride, bromide, and iodide,2,4-dichlorobenzyltris(Z-cyanoethyl) phosphonium chloride, bromide andiodide, 2,5-dichlorobenzyltris(2 cyanoethyl)phosphonium chloride,bromide and iodide, 3,4 dichlorobenzyltris(Z-cyanoethyl) phosphoniumchloride, bromide and iodide, 2,4-diiodobenzyltriphenylphosphoniumchloride, bromide and iodide, 2,5 difluorobenzyltriphenylphosphoniumchloride, bromide and iodide, 3,4 dibromobenzyltriphenylphosphoniumchloride, bromide and iodide, 2 hydroxyethyltriphenylphosphoniumchloride, bromide and iodide,tris(2-cyanoeth-yl)-2-hydroxyethylphosphonium chloride, bromide andiodide, tributylbenzylphosphonium chloride, bromide and iodide, tributylvinylphosphonium chloride, bromide and iodide, bis(2-hydroxypropyl)diphenylphosphonium chloride, bromide and iodide,2-hydroxypropylmethyldiphenylphosphonium chloride, bromide and iodide,tributyl-2,4-dichlorobenzylphosphonium chloride, bromide and iodide, 2,5dichlorobenzylphosphonium chloride, bromide and iodide, 3,4-dichlorobenzylphosphonium chloride, bromide and iodide, tris(2cyanoethyl)-o-vinylbenzylphosphon-ium chloride, bromide and iodide,tris(2 cyanoethyl)-p-vinylbenzylphosphonium chloride, bromide andiodide, tris(2-cyanoethyl)-m-vinylbenzylphosphonium chloride, bromideand iodide, triphenyl-o, m and p-vinylbenzylphosphonium chloride,bromide and iodide, tris(2-carboxyethyl)phenylphosphonium chloride,bromide and iodide, bis(2-carboxyethyl)bis(2 cyanoethyl)phosphoniumchloride, bromide and iodide, tributyl-(o, m andp-vinylbenzyl)phosphonium chloride, bromide and iodide,ethyltriphenylphosphonium chloride, bromide and iodide,2-hydroxyethyltriphenylphosphonium chloride, bromide and iodide,tributyl[2-(2-methyl 1 imidazolyl)ethyl1phosphonium chloride, bromideand iodide, tricyclohexyl[Z-(Z-methyll-imidazolyl)ethyllphosphoniumchloride, bromide and iodide, tributyl(diethylaminoethyl)phosphoniumchloride, bromide and iodide,2-butenylbis(Z-cyanoethyl)phenylphosphonium chloride, bromide andiodide, 4-octenyl(2- hydroxyethyl)methylphenylphosphonium chloride,bromide and iodide, 2-cyanoethyl(4-cyanobutyl)diphenylphosphoniumchloride, bromide and iodide, diethylphenyl- (4-hydroxybutyl)phosphoniumchloride, bromide and iodide,allylbenzyl(8-hydroxyoctylmethylphosphonium chloride, bromide andiodide, carboethoxyethyl(8-cyanooctyl) diphenylphosphonium chloride,bromide and iodide, bis- (8-carboxyoctyl)dimethylphosphonium chloride,bromide and iodide, bis(2 cyanoethyl) (p-bromobenzyl)phenylphosphoniumchloride, bromide and iodide, bis(2-cyanoethyl)(4-carboxybutyl)phenylphosphonium chloride, bromide and iodide,bis(2-cyanoethyl)naphthylphenylphosphonium chloride, bromide and iodide,diphenylmethyl [4-(2-methyl 1 imidazolyl)butyl]phosphonium chloride,bromide and iodide, tris(2-cyanoethyl)(Z-methylnaphthyl)phosphoniumchloride, bromide and iodide, tris- (2cyanoethyl)-2,4-(dibromobenzyl)phosphonium chloride, bromide and iodide,methyldiphenyl[8-(2-methyl-1- imidazolyl)octyl]phosphonium chloride,bromide and iodide, diphenylmethyl(p-iodobenzyl)phosphonium chloride,bromide and iodide, tris(2-cyanoethyl) (3-chloro-2-methyl-naphthyl)phosphonium chloride, bromide and iodide,tributyldimethylaminoethylphosphonium chloride, bromide and iodide,Z-carboethoxypropyltriphenylphos= phonium chloride, bromide and iodide,carbooctoxymethyltriphenylphosphonium chloride, bromide and iodide,dibutylaminoethyltrimethylphosphonium chloride, bromide and iodide,dibenzyl(p-chlorobenzyl)propylphosphonium chloride, bromide and iodide,cyanomethyltrimethylphosphonium chloride, bromide and iodide,butyltris(p-nitrobenzyl)phosphonium chloride, bromide and iodide, tetra-B-carboxypropenyl-l-phosphonium chloride, bromide and iodide,tetra-3-carboxypropenyl-l-phosphonium chloride, bromide and iodide,trimethyl-3-carboxypropenyl-l-phosphonium chloride bromide and iodide,triphenyl-Z-carboxyvinyl-l-phosphonium chloride, bromide and iodide, andthe like, mixtures thereof, other phosphonium halides having mixedsubstituents and the like.

Examples of compounds represented by Formula II, above, i.e. the novelcompounds of the instant invention, include tris(2-cyanoethyl) 2carbomethoxyvinylphosphonium chloride and bromide,tris(2-cyanoethyl)-2-carbomethoxypropenyl-3-phosphonium chloride andbromide, triphenyl-4-carbomethoxybutenyl 4 phosphonium chloride andbromide, triphenyl-Z-carbomethoxypropenyl- 3-phosphonium chloride andbromide, tributyI-Z-carbomethoxypropenyl-3-phosphonium chloride andbromide, tributyl-S-carbomethoxypentenyl-Z-phosphonium chloride andbromide, tributyl 2 carbomethoxyhexenyl-l-phosphonium chloride andbromide, tris(2-cyanoethyl)-2- carboethoxyvinyl phosphonium chloride andbromide, tris(2-cyanoethyl)-3-carbobutoxypropenyl 3 phosphonium chlorideand bromide, dioctylvinyl 2 carbomethoxypropenyl-3-phosphonium chlorideand bromide, tris- (2-hydroxyethyl) 2 carbomethoxypropenyl 3 phosphoniumchloride and bromide, bis(1-carboxypropyl)methyl-2-carbomethoxypropenyl-3-phosphonium chloride and bromide,methylnaphthylphenyl-2-carbomethoxypropenyl-3-phosphonium chloride andbromide, dibenzylethyl-2-carbomethoxypropenyl 3 phosphonium chloride andbromide, p-nitrobenzyltris(2-carbomethoxypropenyl-3) phosphoniumchloride and bromide, tris(dimethylaminoethyl)-2-carbomethoxypropenyl 3phosphonium chloride and bromide,tris(2-carbomethoxyethyl)-2-carbomethoxypropenyl-3-phosphonium chlorideand bromide, tris(2-cyanoethyl 3 carboxypropenyl 1 phosphonium chlorideand bromide, tributyl-Z-carboxyvinyl phosphomum chloride and bromide,tetra(2-cyanoethyl)phosphonium bromide, mixtures thereof, othercompounds having mixed substituents and the like.

It is also within the scope of the present invention to incorporate suchingredients as plasticizers, dyes, pigments, stabilizers, antioxidants,antistatic agents and the like to our novel compositions.

The following examples are set forth for purposes of illustration onlyand are not to be construed as limitations on the present inventionexcept as set forth in the appended claims. All parts and percentagesare by weight unless otherwise specified.

Any appropriate flame-retardance test may be used to determine the flameretardance properties of any specific compound. One test which isreasonably efiicient is that designated as a modified version of ASTMtest D-635- 56T. The specifications for this test are: a specimen, 5" inlength, 0.5" in width and 0.045" in thickness, is marked at the 1" and4" lengths and is then supported with its longitudinal axis horizontaland its transverse axis inclined at 45 to the horizontal. A Bunsenburner with a 1'' blue flame is placed under the free end of the stripand is adjusted so that the flame tip is just in contact with the strip.At the end of 30 seconds, the flame is removed and the specimen isallowed to burn. If the specimen does not continue to burn after thefirst ignition it is immediately recontacted with the burner for another30-second period. If, after the two burnings, the strip is not burned tothe 4" mark, the specimen is designated as self-extinguishing orflame-retardant.

EXAMPLE 1 10 results of these examples are set forth in Table 1 below.In each instance, the resultant plastic-monophosphonium halide mixturepassed the flame-retardance test and was designated as flame andfire-retardant. In the table,

PE=p0lyethylene; PP=polypropylene; PMMA=poly- (methylmethacrylate);PA=poly(acrylic acid); PS=poly- (styrene); PF=polyformaldehyde;CA=cellulose acetate; -PC=polycarbonate (Bisphenol A-phosgene reactionproduct); AN=acrylonitrile; ST=styrene and BD=butadiene. The term nylonrefers to the reaction product of adipic acid and hexamethylene diamine.

TABLE I Flame retardant Poly- Per- Ex mer R R R R X cent 2 Q Q Q Br 15 3PP Sameasabove CH I 4 PP do-. CHsCH-z Br 5 PP do CHa(CHz)z BI 6 PE -doCH2=CHCH2 Br 30 7 PP .do ..do ..do C1 20 8 PE do do v.do Same as aboveBr 9 PE do. do I 15 10. PP .do do ..do d0 I 15 11..... PE do ..do ..doBr 20 OQN CH2 12 PP Cl 15 C1 -CH2 13..- PE do do d0 Same as above Cl 1514 PE do .do do N Br 20 CH3CHzOCCHz 15- PE NCCHzCHz NCCHzCHz NCCH2CH2OH: I 10 16 PM NCCHzCHz NCCHECHZ NCCHzCHz CH3 I 10 17.--..- PE NCCHzCHaNCOHzCHz NCOHzCHz CHQCHZ Br 20 18"-.- PE NCCHzCHg NCCHzCHz NCCHzCHz CH(CH2)7 Br 19 PE NCCH2OH2 NCCH2CH2 NCCHzCHz CH2=CH 2 Br 20 20"--- P A.NCCH2CH3 NCGHZCHZ CNCH2CH2 CH2=CHCH2 BI 20 21... NCCHzCHz NCCHzCHzNCCHzCHz CH2= CHCH: C1 30 22 PE NCCHzCHz NCCHZCH? NCCH2CH2 Q CH 01 2523.. PE NCCHzCHz NCCHzCHz NCCHzCH-z Same as above Br 30 24....-- PENCCHzCH: NCCHzCHz NCCH2CH: I 15 Cl- CH2 25.--" PP NCCHzCHz NCCHzCHzNCCH2CH2 Same as above I 15 26-.... PE NCCHzCHa NCCHzCHz NCCHzCHz 2 4 37yMixedlisomers of: Cl 10 2:5 50Z 3,4=13% -CH2 27...--- PE Q Q Q HOCH2CH2Br 15 28.-.-. PE C1 20 CH2 CH2 CHz CH:

29 PE CHaCHzCHzCHz CHaCHzCHzCHz CHaCHzCHzCHz Same as above Cl 30 30 PMMACHaCHzCHzCHz CH3CH2CH2CH2 CHzCHzCHzCHz d0 C1 30 PE CHaCHzCHzCHzCHaCHzCHzCHz CH3CH2CH2CH2 CH2: CH B1 30 32...... PM CHzCHzCHzCHaCHaCHzCHzCHz CHaCHzCHzCHz CHz= CH B1 30 33.. PE CHaCHCHz CH3$HCH2 Q Q Br20 OH O 34 PE Same as above CH3 Same as above Same as above I 20 35--...PE NCCHzCHz NCCHzCHz NCCHzCHz HOCHzCHz Br 20 36 PE CHaCHzCHzCHzCH3CH2CH2CH3 CH CHzCHzCH; C1 15 (HQ-4H2 TABLE I-Continrued Flameretardant Poly- Per- Ex. mer R R R R X cent 92...-.. PS C4119 C4119 C4HB1 CI'IQ 93---" PMMA O O CNCHzCHg O C1 94--. PF Q Q Q H3COzCCH=CH Br 95.PS Same as above HO OH: H CO CCH=CH Br 10 Cl -CH:

96.-. PP 05H 05H 05H HaCOzCCH=CH B1 97--. Nylon HOCH: NCCHzCH; HCgOzC("3CHg CHz -CH Cl 25 98..." PC HaCOrCMfiCIh CH3 CH3 CH3 B1 2098A.-. PS NCCHzCHz NCCHzCHz NCCHzCHg CH3 I 5 983... PS CH3 C1 10 01--CH: 01- --CH; Cl CH3 l l I C1 C1 C1 1 Mixture of BD-AN (10-75%) andAN-STY (25-90%). 2 MMA/ST/AN 71/19/10.

3 Mixture of BD/AN (10/75) and AN/STY (25/90), U.S. Patent No.2,439,202.

4 Blend of PS(90%) and BD-STY (75/25)(10%).

EXAMPLE 99 To a suitable reaction vessel equipped with gas inlet andoutlet, thermometer and stirrer are added 19.4 parts ofmethyl-Z-(chloromethyl) acrylate in parts of acetonitrile and 27 partsof tris(2-cyanoethyl) phosphine with stirring. A vigorous exothermoccurs and a solid precipitates. The reaction mixture is kept in anitrogen atmosphere for two hours. At the end of this time the solid isremoved by filtration, washed With acetonitrile and anhydrous ether anddried in vacuum. 34 parts of tris(2-cyanoethyl)-2-carbomethoxypropenyl 3phosphonium chloride are recovered (73% yield). The chloride is a whitesolid having a melting point of 151-154 C. dec.

TABLE II Tempera- Time, Yield, Ex. Tertiary phosphine Halide ture, 0.hours Solvent percent Product 100.... 26 parts of triphenyl ph0sphine.13 parts of methyl-2-(chl0r0- 81 2. 5 Acetonitrile.-. 97Tripheny1-2-earbomethoxymethyl) aerylate. propenyl-3-phosphopiun1chloride. 101--.. 27 parts of tributyl phosphine... 19 parts ofmethyl-Z-(ehloro- 75 2 .....do 74 Tributy1-2-earbomethoxymethyl)acrylate. propenyl-3-phosphonium chloride. 102.-.. 30 parts ofdimethyloetyl 17 parts of 3-ehlor0aerylie 4 .....d0 80 (Z-carboxyvinyl)dimethylphosphine. acid. oetyl phosphonium chloride. 103-... 26 parts ofdivinyhnethyl 16 parts of butyl-Z-(ehloro- 50 4 do 76Z-earbobutoxypropenyl-Ziphosphine. methyl) aerylate.nifithyildivinylphosphonium e on e. 104.... 28 parts of triseyanomethyl15 parts of 4-chloro-3-butenoie 2 ..do 823-earboxypropenyl-1-triscyanophosphine. acid. rriiethylphosphoniumchlorl e. 105.... 17 parts of 3-hydroxyoetyldipro- 8 parts of methyl-3-2 5 --...do 79 2-earbomethoxyvinyl-3- penylphosphiue. ehloroaerylate.hydroxyoctyl-dipropenyl- 3-phosphoniu1n chloride. 106.-.. 10 parts oftrinaphthyl 6 parts of methyl 5-ul1loro4- 73 3. 5 .-...do 834-carbomethoxy-l-buten l-ylphosphine. 4-pentenoate. lZllllilap'lthylphosphonium c on e. 107.-.. 21 parts of benzyldiplienyl 11 parts of3-bronioaerylie 68 4 ....d0 71 Benzyl-2-earboxyvinylphosphine. acid.diphenyl phosphomum bromide. 108.... 36 parts of tris(2,4-diehloro- 20parts of ethyl 3-bromo 77 2 .....do 73 2- carboethoxyvinyl-tris(2, 4-

benZyDphosphine. aerylate. 1tshlorogenzyl) phosphonium romi e. 109....15 parts of bis(p-nitroplwuetlwl) 0 parts of ethyl Q-(Di'muoethyl) 80 1.5 .do 87 .Z-oerboethoxypropenyl-3- methyl phospliinel nev /later methylbis(p-nitrophenethyl) phosphonium bro milder TABLE II.Cn1binued Tempera-Time, Yield, Ex. Tertiary phosphine Halide ture, 0. hours Solventpercent Product 110...- 26 parts of tris(dimethy1- parts of ethylZ-(bromo- 75 3 ..d0 75 2-earboethoxy-3-tris (dimethyl aminoethyl)phosphine. ethyl) aerylate. iamminogthyl) phosphonium I'OIl'll e.111.... 9 parts of tris(carbomethoxy- 6 parts of methyl 4-bromo- 73 3Butanol 82 4-cerbomethoxy-1-buten-1- methyl) phosphine. 4-penten0ate.yl-tn's (carbomethoxymethyl) phosphonium bromide. 112.... 5 parts oftrivinyl phosphine 3 parts of 2 ehl0r0aerylic acid.. 78 2. 5Aeetonitrile 91 l-carboxyvinyltrivinyl phosphonium chloride. 113.-.. 42parts of his (Z-carboxyethybparts of 4-ehloro-3-butenoic 65 4 .-d0 88Bis (Z-earboxyethyl) 3-earboxyphenyl phosphine. acid. propenyl-l-phenylphosphonium chloride. 114.... 17 parts of dimethyl (p-vinyl- 8 parts ofpropy1-3-bromo- 4 .do 93 2-0arbopropoxyvinyl-dimethylbenzyl) phosphine,aerylate. g-vinybenzyl phosphonium romi e. 115.... 19 parts oftris(p-bromobenzyl)- 10 parts of ethyl-2-(2-ehloro- 4 ....do 712-0arboethoxy-l-buten-i-ylphosphine. ethyl) aerylate. tris(p:bromobenzyl) phosphonium chloride. 116.... 1 parts oftris(2-dimethyl- 1 parts of ethyl 5-bromo-4- 60 4 d0 524'earboethoxy-l-buterrfl-ylaminobutyl) phosphine. pentenoate. tris(2-dimethylamiriobutyl) phosphouium bromide. 117.... 14 parts oftris(1-earboetl10xy- 8 parts of 3ehloroecrylie acid.. 75 3 .....doTris(1-carboethoxypropyl)-2- propyl) phosphine. eaixlrlboi yvinylphosphom'um C On e. 118.... 25 parts of tris(2 :yanoethyl)- 30 parts ofZ-bromopropim 80 4 Acetonitrile... TetraQeyanoethyDphosphosphine.nitrile. phonium bromide.

1 0.1 part hydroquinone added to retard polymerization. We claim:3,322,861 5/1967 Gillham et a1. 260-465.8 X

1. Tetra-Z-cyanoethylphosphonium bromide.

References Cited UNITED STATES PATENTS 3,475,479 10/1969 Vullo 260465.8

OTHER REFERENCES Grayson et al.: J.A.C.S., vol. 82, 1960, pp. 3919-3924.

JOSEPH P. BRUST, Primary Examiner Grayson et a1. 260--465.8 X Grayson eta1. 26o 465.8

Rauhut 260465.8 X 260-45.7, 45.8, 45.85, 45.9, 45.95, 309, 403, 464,465, Barrett 26o 465.8 465.1, 465.4, 469, 471, 482, 484, 485, 486, 487,488, 515,

Grayson et a1. 260-465.5 X 518, 526, 534, 537, 539, 570.8, 583

